Synthesis of Radiolabeled [14C]Rimsulfuron and Stable Isotope Labeled Rimsulfuron-[M + 3] to Support Crop Metabolism Studies for Reregistration.

Rimsulfuron is a sulfonylurea herbicide that controls grass and broadleaf weeds in maize, potatoes, fruits, nuts, and other crops. It can also be used as a burndown herbicide to clear invasive weed species along roadsides and other nonagricultural land. Rimsulfuron acts as an acetolactase synthase (ALS) inhibitor, blocking the synthesis of essential amino acids required for plant growth. As is common practice, rimsulfuron has been subject to periodic reviews by regulatory agencies for reregistration since its introduction into the market in the early 1990s. The goal of these reviews is to ensure that the herbicide carries out its intended use without creating adverse side effects to humans and the environment. Since scientific methods are continually evolving and being developed, global regulatory agencies can require additional studies to address data gaps for pesticide renewals. During this reregistration process for rimsulfuron, a new confined rotational crop study was required to address a data gap requested by the European Food Safety Authority (EFSA). Consequently, the corresponding pyridine and pyrimidine radiolabeled [14C]rimsulfuron and [M + 3] stable isotopes of rimsulfuron were synthesized for this study to support the reregistration process.

Synthesis, stability and insecticidal activity of 2-arylstilbenes.

BACKGROUND: A chemical scaffold-hopping approach from known 3-hydroxyl-3-methylglutaryl-CoA (HMG-CoA) reductase inhibitors identified (E/Z)-2-arylstilbenes as novel insecticidal hits against two lepidopteran species, Spodoptera exigua and Trichoplusia ni. A structure-activity relationship (SAR) study of the aryl substituents and the E/Z conformations was carried out in an effort to improve insecticidal potency. RESULTS: A series of (E/Z)-2-arylstilbenes was prepared and separated to evaluate their insecticidal potency against lepidopterous species in diet-feeding assays. The results showed that the (Z)-2-arylstilbenes were more active than their corresponding (E)-isomers, and a stereoselective synthesis was utilized to expand the SAR of the (Z)-2-arylstilbenes. (Z)-4'-Fluoro-3'-methyl-2-(2,4-difluorostyryl)-4-fluoro-5-methoxy-1,1'-biphenyl was the most potent analog in this study with strong activity against S. exigua, T. ni, Helicoverpa zea, Plutella xylostella and Pseudoplusia includens. CONCLUSION: The (Z)-2-arylstilbenes were found to have strong insecticidal potency against five lepidopteran species. Ultimately, synthetic efforts could not improve insecticidal potency to commercial levels, and a lack of UV stability led to efforts being discontinued. © 2019 Society of Chemical Industry.